CN110272623B - Preparation method of polyamide flame-retardant powder material for laser sintering - Google Patents
Preparation method of polyamide flame-retardant powder material for laser sintering Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention provides a preparation method of a polyamide flame-retardant powder material for laser sintering, which comprises the following steps: the following components in parts by mass: adding 100 parts of polyamide resin, 1-30 parts of flame retardant, 0-1 part of antioxidant and 400-2000 parts of solvent into a closed high-pressure reaction kettle to form a mixture, vacuumizing, and introducing inert protective gas; continuously stirring the mixture, heating the mixture at the heating rate of 0.5-3 ℃/min to the reaction temperature of 120-; and (3) uniformly mixing the polyamide flame-retardant powder with a powder flow assistant to prepare the polyamide flame-retardant powder material for laser sintering. The preparation method of the polyamide flame-retardant powder material provided by the invention has the advantages of simple process, good flame-retardant effect of the material, high yield and low cost.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a preparation method of a polyamide flame-retardant powder material for laser sintering.
Background
Laser sintering is a method for manufacturing three-dimensional objects by selectively fusing layers of powder, which allows to obtain a three-dimensional entity without using tooling but by laser sintering multiple superposed layers of powder according to a three-dimensional image of the object to be produced. This process is mainly performed using thermoplastic polymers, and patents US6136948 and WO9606881 describe in detail such a process for manufacturing three-dimensional objects using powdered polymers.
Polyamide is a thermoplastic engineering plastic with excellent performance, has better mechanical properties and chemical corrosion resistance, and is widely applied in the industrial field. Compared with the traditional injection molding method, the method for manufacturing the polyamide three-dimensional part by using the laser sintering technology has the advantages of short production period, high flexibility, simple process and the like, and has wide application space. However, the polyamide material has no flame retardant property, generates a large amount of dense smoke and molten drops in the combustion process, and is very easy to spread flame, so that the application of the polyamide material in special fields such as aerospace, automobile manufacturing, electronic and electric appliances and the like is greatly limited.
Patent CN106987116A discloses a method for preparing a polyamide flame retardant material by mixing polyamide powder with a flame retardant, which has a simple process but also has many disadvantages: 1. the polyamide powder and the flame retardant are difficult to be uniformly mixed; 2. the addition of a large amount of flame retardant into the polyamide powder reduces the flowability of the powder and affects the sintering process; 3. laser energy directly acts on the flame retardant in the sintering process, so that the flame retardant is decomposed, and the flame retardant effect is influenced; 4. some components in the flame retardant are easily decomposed by heat energy and laser, so that generated low molecular substances are condensed in a sintering equipment cavity and a window mirror, the function and the service life of the equipment are influenced, meanwhile, the penetration of laser energy is hindered, and the mechanical property and the effective printing height of a workpiece are greatly reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a polyamide flame-retardant powder material for laser sintering, which comprises the steps of coating a flame retardant in polyamide powder by a solvent precipitation method, uniformly dispersing the flame retardant in the polyamide powder as a nucleating agent, uniformly mixing the polyamide powder and the flame retardant, tightly combining the polyamide powder and the flame retardant, indirectly avoiding the decomposition of the flame retardant in the sintering process, improving the flame-retardant effect, ensuring the fluidity of the polyamide powder due to less addition of the flame retardant, and leading the prepared polyamide powder material to have concentrated particle size distribution, high yield, low cost, high sphericity of the obtained powder and good fluidity, and be particularly suitable for a laser sintering process.
A preparation method of a polyamide flame-retardant powder material for laser sintering comprises the following steps:
(1) the following components in parts by mass are mixed: adding 100 parts of polyamide resin, 1-30 parts of flame retardant, 0-1 part of antioxidant and 400-2000 parts of solvent into a closed high-pressure reaction kettle to form a mixture, vacuumizing, and introducing inert protective gas;
(2) under the condition of continuously stirring the mixture, heating the mixture at the heating rate of 0.5-3 ℃/min to the reaction temperature of 120-;
(3) and carrying out solid-liquid separation on the powder suspension, drying and grinding, and screening the polyamide flame-retardant powder with the particle size of 10-120 microns.
(4) And uniformly mixing the polyamide flame-retardant powder with a powder flow aid to prepare the polyamide flame-retardant powder material for laser sintering.
Preferably, the polyamide resin is one or more of PA12, PA1212, PA6, PA610, PA66, PA612, PA46, PA1012, PA56, PA513, PA514 and PA 1010.
Preferably, the flame retardant is one or more of alkyl phosphate series flame retardants, nitrogen series flame retardants, phosphorus series flame retardants and nitrogen and phosphorus series flame retardants.
Preferably, the particle size of the flame retardant is 1-50 microns.
Further preferably, the particle size of the flame retardant is 15-30 microns.
Preferably, the solvent in step (1) is one or more of methanol, ethanol, propanol, water, ethylene glycol, butanone, formamide and acetamide.
Preferably, the powder flow assistant is one or more of silicon dioxide, silicon carbide, aluminum oxide, calcium oxide, titanium dioxide and calcium carbonate with the particle size range of 5-100 nm.
Preferably, the powder flow assistant is a hydrophobic flow assistant with the surface subjected to organic treatment.
Preferably, the antioxidant is composed of a hindered phenol antioxidant and a phosphite antioxidant, wherein the hindered phenol antioxidant is 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2, 6-di-tert-butyl-4-methyl-phenol, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide), and the phosphite antioxidant is 2, 2 ' -ethylidene bis (4, 6-di-tert-butylphenyl) fluorophosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4 ' -biphenylbis-phosphite.
Preferably, the mass fraction of the hindered phenol antioxidant in the antioxidant is 40-90%, and the balance is phosphite antioxidant.
The preparation method of the polyamide flame-retardant powder material for laser sintering provided by the invention has the following beneficial effects:
1. according to the polyamide flame-retardant powder prepared by the method, the flame retardant is uniformly dispersed in the polyamide base material, so that the defects of phase separation and poor flame-retardant effect caused by nonuniform distribution of the flame retardant are overcome;
2. the polyamide flame-retardant powder prepared by the solvent method has narrow particle size distribution, high yield, remarkably reduced manufacture, higher powder sphericity and better fluidity.
3. After the powder is mixed with the hydrophobic nano flow additive, the flow additive is coated on the surface of the powder particles, so that the connection between the polyamide particles and the outside is isolated, the problem of easy water absorption of the polyamide material is solved, the fluidity and the stability of the powder material are further improved, and the powder material can better meet the powder laying requirement of laser sintering.
4. The flame retardant is completely coated by the polyamide, and the low-melting-point component in the flame retardant is not decomposed by heating in the sintering process, so that the generation of volatile matters is reduced; in the laser sintering process, laser directly acts on polyamide, so that the problem that the polyamide absorbs laser energy due to the existence of a flame retardant is well solved, the material is more fully melted, and the mechanical and mechanical properties are excellent; meanwhile, the flame retardant coated in the polyamide powder particles cannot be separated from the polyamide, so that the decomposition caused by overhigh instantaneous energy under the action of laser is reduced, and the flame retardant effect is ensured.
Detailed Description
The present invention is described in further detail below by way of specific examples.
Example 1
Putting 8Kg of PA1212 material, 2Kg of flame retardant OP1230 and 100Kg of ethanol into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen until the pressure is 0.3MPa, exhausting the nitrogen, raising the temperature in the kettle to 150 ℃ at a heating speed of 2 ℃/min under continuous stirring, and keeping the temperature at the temperature for 60 min; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.8 ℃/min, increasing the flow rate of the cooling water so that the temperature in the kettle is reduced to room temperature at a rate of 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain a polyamide 1212 flame-retardant powder sample. A polyamide 1212 flame retardant powder material was prepared by uniformly mixing a 9kg sample of polyamide 1212 flame retardant powder with 45g of silicon dioxide having a particle size of 20nm and a surface modified with a silazane derivative.
Comparative example 1
Adding 8Kg of PA1212 material and 100Kg of ethanol into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen until the pressure is 0.3MPa, exhausting the nitrogen, continuously stirring, raising the temperature in the kettle to 150 ℃ at a heating speed of 2 ℃/min, and preserving the heat for 60min at the temperature; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.8 ℃/min, increasing the flow rate of the cooling water so that the temperature in the kettle is reduced to room temperature at a rate of 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain a polyamide 1212 powder sample. A9 kg sample of polyamide 1212 powder was homogeneously mixed with 45g of silica having a particle size of 20nm to prepare a polyamide 1212 powder material.
Example 2
Adding 8Kg of PA6 material, 2Kg of flame retardant OP1230, 60Kg of methanol and 40Kg of water into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen till the pressure is 0.3MPa, exhausting the nitrogen, continuously stirring, raising the temperature in the kettle to 155 ℃ at the heating speed of 2 ℃/min, and keeping the temperature at the temperature for 90 min; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.6 ℃/min, increasing the flow of the cooling water so that the temperature in the kettle is reduced to room temperature at a rate of 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain a polyamide 6 flame-retardant powder sample. A polyamide 6 flame-retardant powder material was prepared by uniformly mixing a 9kg polyamide 6 flame-retardant powder sample with 63g of silicon dioxide having a particle size of 20nm and a surface modified with a silazane derivative.
Comparative example 2
Adding 8Kg of PA6 material, 60Kg of methanol and 40Kg of water into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen until the pressure is 0.3MPa, exhausting the nitrogen, continuously stirring, raising the temperature in the kettle to 155 ℃ at a heating speed of 2 ℃/min, and keeping the temperature at the temperature for 90 min; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.6 ℃/min, increasing the flow rate of the cooling water so that the temperature in the kettle is reduced to room temperature at a rate of 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain a polyamide 6 powder sample. A polyamide 6 powder material was prepared by uniformly mixing a 9kg sample of polyamide 6 powder with 63g of silicon dioxide having a particle size of 20nm and a surface modified with a silazane derivative.
Example 3
Putting 8Kg of PA610 material, 2Kg of flame retardant OP1230, 80Kg of methanol and 20Kg of water into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen till the pressure is 0.3MPa, exhausting the nitrogen, continuously stirring, raising the temperature in the kettle to 155 ℃ at the heating speed of 2 ℃/min, and keeping the temperature at the temperature for 60 min; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.7 ℃/min, increasing the flow rate of the cooling water so that the temperature in the kettle is reduced to room temperature at 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain the polyamide 610 flame-retardant powder sample. A polyamide 610 flame retardant powder material was prepared by uniformly mixing 9kg of a polyamide 610 flame retardant powder sample with 63g of silicon dioxide having a particle size of 20nm and a surface modified with a silazane derivative.
Comparative example 3
Adding 8Kg of PA610 material, 80Kg of methanol and 20Kg of water into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen till the pressure is 0.3MPa, exhausting the nitrogen, raising the temperature in the kettle to 155 ℃ at a heating speed of 2 ℃/min under continuous stirring, and preserving the heat for 60min at the temperature; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.7 ℃/min, increasing the flow rate of the cooling water so that the temperature in the kettle is reduced to room temperature at 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain a polyamide 610 powder sample. A9 kg sample of polyamide 610 powder was homogeneously mixed with 63g of silica having a particle size of 20nm to prepare a polyamide 610 powder material.
Example 4
Adding 8Kg of PA66 material, 2Kg of flame retardant OP1230, 45Kg of methanol and 55Kg of water into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen till the pressure is 0.3MPa, exhausting the nitrogen, continuously stirring, raising the temperature in the kettle to 160 ℃ at a heating speed of 2 ℃/min, and keeping the temperature at the temperature for 120 min; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.5 ℃/min, increasing the flow rate of the cooling water so that the temperature in the kettle is reduced to room temperature at a rate of 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain a polyamide 66 powder sample. A polyamide 66 flame-retardant powder material was prepared by uniformly mixing a 9kg sample of polyamide 66 powder with 72g of silica having a particle size of 20nm and a surface modified with a silazane derivative.
Comparative example 4
Adding 8Kg of PA66 material, 45Kg of methanol and 55Kg of water into a 100L reaction kettle, vacuumizing, introducing high-purity nitrogen until the pressure is 0.3MPa, exhausting the nitrogen, continuously stirring, raising the temperature in the kettle to 160 ℃ at a heating speed of 2 ℃/min, and preserving the heat at the temperature for 120 min; and then cooling by using cooling water, so that the temperature in the kettle is reduced to 80 ℃ at a cooling rate of 0.5 ℃/min, increasing the flow rate of the cooling water so that the temperature in the kettle is reduced to room temperature at a rate of 2 ℃/min, taking out the materials, carrying out centrifugal separation, drying, grinding and screening to obtain a polyamide 66 powder sample. A9 kg sample of polyamide 66 powder was homogeneously mixed with 72g of silica having a particle size of 20nm to prepare a polyamide 66 powder material.
Particle size analysis was performed on the polyamide powder samples obtained in examples 1 to 4 and comparative examples 1 to 4, respectively, and the mechanical properties and flame retardant properties of the obtained articles were measured by sintering the powder samples using ST252 laser sintering equipment in the dawn gaku.
As can be seen from the table, the particle size distribution of the polyamide flame-retardant powder prepared by the invention becomes more concentrated, the tensile strength of the laser sintering product is basically close to that of pure polyamide, and the polyamide flame-retardant powder has good flame-retardant property.
In the invention, the flame retardant is added not only as a flame retardant component, but also as a crystal blank to participate in the cooling and recrystallization process of polyamide in the cooling and crystallization process of polyamide, so that the original homogeneous nucleation is changed into heterogeneous nucleation, polyamide materials in a solution grow into powder particles of the polyamide-coated flame retardant on the surface of the flame retardant, the crystallization process is more stable and ordered, and the particle size distribution of the polyamide flame retardant powder is more uniform.
According to the polyamide flame-retardant powder prepared by the invention, the flame retardant is uniformly dispersed in the polyamide base material, so that the defects of phase separation and poor flame-retardant effect caused by nonuniform distribution of the flame retardant are overcome; the polyamide flame-retardant powder prepared by the solvent method has narrow particle size distribution, high yield, remarkably reduced manufacture, higher powder sphericity and better fluidity. After the powder is mixed with the hydrophobic nano flow additive, the flow additive is coated on the surface of the powder particles, so that the connection between the polyamide particles and the outside is isolated, the problem of easy water absorption of the polyamide material is solved, the fluidity and the stability of the powder material are further improved, and the powder material can better meet the powder laying requirement of laser sintering. The flame retardant is completely coated by the polyamide, and the low-melting-point component in the flame retardant is not decomposed by heating in the sintering process, so that the generation of volatile matters is reduced; in the laser sintering process, laser directly acts on polyamide, so that the problem that the polyamide absorbs laser energy due to the existence of a flame retardant is well solved, the material is more fully melted, and the mechanical and mechanical properties are excellent; meanwhile, the flame retardant coated in the polyamide powder particles cannot be separated from the polyamide, so that the decomposition caused by overhigh instantaneous energy under the action of laser is reduced, and the flame retardant effect is ensured.
Claims (8)
1. The preparation method of the polyamide flame-retardant powder material for laser sintering is characterized by comprising the following steps of:
(1) the following components in parts by mass are mixed: adding 100 parts of polyamide resin, 1-30 parts of flame retardant, 0-1 part of antioxidant and 400-2000 parts of solvent into a closed high-pressure reaction kettle to form a mixture, vacuumizing, and introducing inert protective gas, wherein the solvent is mixed solution of ethanol and water or mixed solution of methanol and water;
(2) under the condition of continuously stirring the mixture, heating the mixture at a heating rate of 0.5-3 ℃/min to a reaction temperature of 120-: cooling with cooling water to 70-90 deg.C at a rate of 0.1-1.5 deg.C/min, and cooling to room temperature at a rate of 1.5-3.0 deg.C/min;
(3) carrying out solid-liquid separation on the powder suspension, drying and grinding, and screening polyamide flame-retardant powder with the particle size of 30-120 microns;
(4) and uniformly mixing the polyamide flame-retardant powder with a powder flow aid to prepare the polyamide flame-retardant powder material for laser sintering.
2. The method for preparing polyamide flame-retardant powder material for laser sintering according to claim 1, wherein the polyamide resin is one or more of PA12, PA1212, PA6, PA610, PA66, PA612, PA46, PA1012, PA56, PA513, PA514 and PA 1010.
3. The method for preparing the polyamide flame-retardant powder material for laser sintering according to claim 2, wherein the flame retardant is one or more of a nitrogen flame retardant, a phosphorus flame retardant and a nitrogen-phosphorus series.
4. The method for preparing polyamide flame-retardant powder material for laser sintering according to claim 3, wherein the particle size of the flame retardant is 1-50 μm.
5. The method for preparing polyamide flame-retardant powder material for laser sintering according to claim 4, wherein the powder flow assistant is one or more of silicon dioxide, silicon carbide, aluminum oxide, calcium oxide, titanium dioxide and calcium carbonate with the particle size of 5-100 nm.
6. The method for preparing polyamide flame-retardant powder material for laser sintering according to claim 4 or 5, wherein the powder flow aid is a hydrophobic flow aid whose surface is organically treated.
7. The method for preparing polyamide flame retardant powder material for laser sintering according to claim 6, wherein the antioxidant comprises hindered phenol antioxidant and phosphite antioxidant, wherein the hindered phenol antioxidant is 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2, 6-di-tert-butyl-4-methylphenol, and the phosphite antioxidant is 2, 2 '-ethylidene bis (4, 6-di-tert-butylphenyl) fluorophosphite or tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylene diphosphite.
8. The method for preparing polyamide flame-retardant powder material for laser sintering according to claim 7, wherein the mass fraction of hindered phenol antioxidant in the antioxidants is 40% -90%, and the balance is phosphite antioxidant.
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